EP2358855B1 - Automatic dishwashing tablet - Google Patents

Description

The present invention is in the field of detergent tablets and relates to phosphate-free detergent tablets and methods for their preparation.

Detergent tablets are widely described in the art and are becoming increasingly popular with consumers because of their ease of use. Tableted detergents and cleaners have a number of advantages over powdered ones: they are easier to dose and to handle and, due to their compact structure, have advantages in storage and transport. Also in the patent literature washing and cleaning agent tablets are thus described comprehensively. A problem which occurs again and again in the application of washing and cleaning-active moldings is the too low disintegration and dissolution rate of the moldings under conditions of use. Since sufficiently stable, i. Form-resistant and fracture-resistant molded body can be produced only by relatively high pressing pressures, there is a strong compaction of the molding constituents and a consequent delayed disintegration of the molding in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process ,

Another problem that particularly occurs with detergent tablets is the often inadequate stability of these tablets against the stresses of packaging, shipping and handling, i. against falling and impact stresses. After pressing, the tablets are fed on conveyor belts of the package, the tablets individually or grouped wrapped with a foil and then packaged in boxes. When filling the tablet meets on a nearly parabolic trajectory from the conveyor belt of the film wrapping machine on the cardboard wall or the previously filled tablets. Here occur in particular in rectangular tablets forces in the longitudinal direction of the tablet, which can lead to Kantenbruch- and Abrieberscheinungen and affect the appearance of the molding or even lead to a complete destruction of the molding structure.

In this context, in particular the development of the tablet hardness after the actual pressing of importance. Tablets which postharden after the actual tabletting, for example during storage and transport, allow the use of lower compression pressures

It is an object of the present invention to provide laundry detergent or detergent tablets which post-cure after production and thus enable the use of lower pressure pressures or the processing of pressure-sensitive washing and cleaning-active constituents, such as, for example, enzymes. The process products should be next to one sufficient hardness further characterized by good decay properties and a low tendency to abrasion.

It has now been found that these objects can be achieved by means of a phosphate-free mono- or multiphase washing or cleaning agent tablet which has in one of its phases a specific mixture of builders and cleaning-active polymers, these phases containing only small amounts of citric acid and no bleaching agents ,

1. a) 15 bis 89,8 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
2. b) 10 bis 84,8 Gew.-% Citrat
3. c) 0,05 bis 20 Gew.-% wasch- oder reinigungsaktives Polymer aus der Gruppe der amphoteren Polymere

enthält, frei ist von Bleichmittel und, bezogen auf das Gesamtgewicht der Phase, weniger als 1 Gew.-% Citronensäure enthält.A first subject of the present application is therefore a single- or multi-phase, phosphate-free detergent or cleaner tablet, characterized in that the phase or one of the phases, based on their total weight,

1. a) 15 to 89.8 wt .-% sodium carbonate and / or sodium bicarbonate
2. b) 10 to 84.8 wt .-% citrate
3. c) 0.05 to 20 wt .-% washing or cleaning-active polymer from the group of amphoteric polymers

contains, is free of bleach and, based on the total weight of the phase, contains less than 1 wt .-% citric acid.

The builder system used in the detergent tablets according to the invention comprises 15 to 89.8% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 84.8% by weight of citrate.

1. a) 15 bis 89,8 Gew.-% Natriumcarbonat
2. b) 10 bis 84,8 Gew.-% Citrat
3. c) 0,05 bis 20 Gew.-% wasch- oder reinigungsaktives Polymer aus der Gruppe der amphoteren Polymere enthält, frei ist von Bleichmittel und, bezogen auf das Gesamtgewicht der Phase, weniger als 1 Gew.-% Citronensäure enthält

ist damit ebenso Gegenstand der vorliegenden Anmeldung wie ein
eine ein- oder mehrphasige, Phosphat freie Wasch- oder Reinigungsmitteltablette, dadurch gekennzeichnet, dass die Phase bzw. eine der Phasen, bezogen auf ihr Gesamtgewicht,

1. a) 15 bis 89,8 Gew.-% Natriumhydrogencarbonat
2. b) 10 bis 84,8 Gew.-% Citrat
3. c) 0,05 bis 20 Gew.-% wasch- oder reinigungsaktives Polymer aus der Gruppe der amphoteren Polymere enthält, frei ist von Bleichmittel und, bezogen auf das Gesamtgewicht der Phase, weniger als 1 Gew.-% Citronensäure enthält

sofern in diesen Verfahren die Gesamtmenge des eingesetzten Natriumcarbonats und Natriumhydrogencarbonats bezogen auf das Gesamtgewicht der Tablettenphase, 15 bis 89,8 Gew.-% beträgt.A single- or multi-phase, phosphate-free detergent or cleaner tablet, characterized in that the phase or one of the phases, based on their total weight,

1. a) 15 to 89.8 wt .-% sodium carbonate
2. b) 10 to 84.8 wt .-% citrate
3. c) contains 0.05 to 20 wt .-% washing or cleaning-active polymer from the group of amphoteric polymers, is free of bleach and, based on the total weight of the phase, less than 1 wt .-% citric acid

is thus as subject of the present application as a
a single- or multi-phase, phosphate-free washing or cleaning agent tablet, characterized in that the phase or one of the phases, based on their total weight,

1. a) 15 to 89.8 wt .-% sodium bicarbonate
2. b) 10 to 84.8 wt .-% citrate
3. c) contains 0.05 to 20 wt .-% washing or cleaning-active polymer from the group of amphoteric polymers, is free of bleach and, based on the total weight of the phase, less than 1 wt .-% citric acid

if, in these processes, the total amount of sodium carbonate and sodium bicarbonate used, based on the total weight of the tablet phase, is 15 to 89.8% by weight.

Mono- or multiphase laundry detergent or detergent tablets according to the invention contain less than 1% by weight of citric acid in their sodium carbonate, citrate and polymer-based phase. In order to further improve the tablet properties such as tablet hardness, friability and post-curing properties, it has proven advantageous to lower the citric acid content in this phase to less than 0.5% by weight and preferably less than 0.1% by weight. Particularly preferred tablet phases are free of citric acid.

1. a) 15 bis 89,8 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
2. b) 10 bis 84,8 Gew.-% Citrat
3. c) 0,05 bis 20 Gew.-% wasch- oder reinigungsaktives Polymer aus der Gruppe der amphoteren Polymere enthält und frei ist von Citronensäure und von Bleichmittel.

A preferred subject of the present application is therefore a single- or multi-phase, phosphate-free detergent or cleaner tablet, characterized in that the phase or one of the phases, based on their total weight,

1. a) 15 to 89.8 wt .-% sodium carbonate and / or sodium bicarbonate
2. b) 10 to 84.8 wt .-% citrate
3. c) contains 0.05 to 20 wt .-% washing or cleaning-active polymer from the group of amphoteric polymers and is free of citric acid and bleach.

The washing or cleaning agent tablets according to the invention contain as washing or cleaning-active polymer c) a polymer from the group of amphoteric polymers.

For the purposes of the present application, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred amphoteric polymers have a monomer unit of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoyxylierte alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group having a positive charge in the partial range of the pH Range of 2 to 11, or salts thereof, with the proviso that at least one radical R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or is at least one amino group having a positive charge.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, lodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

Very particular preference is given to amphoteric polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

H ₂ C = CH- (CH ₂ ) -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) -CH = CH ₂ X ^-

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred amphoteric polymers contain a monomer unit of the general formula

R ¹ HC = CR ² -C (O) -NH- (CH ₂ ) _x -N ⁺ R ³ R ⁴ R ⁵ X ^- ,

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

For the purposes of the present application, very particular preference is given to amphoteric polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

H ₂ C = C (CH ₃ ) -C (O) -NH- (CH ₂ ) _x -N ⁺ (CH ₃ ) ₃ X ^-

In the case of X ^- = chloride, also referred to as MAPTAC (Methyacrylamidopropyl trimethylammonium chloride).

According to the invention, preference is given to using amphoteric polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Preferably used amphoteric polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Particularly preferred amphoteric polymers are selected from the group consisting of the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl ( meth) acrylic acid copolymers and their alkali metal and ammonium salts.

Particular preference is given to amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth ) acrylic acid copolymers and their alkali metal and ammonium salts.

In terms of tablet properties such as tablet hardness, friability and post-curing properties, the amphoteric polymers have proved superior to the anionic polymers, therefore the amphoteric polymers are used.

The tablets (phases) according to the invention contain the three constituents 15 to 89.8% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 84.8% by weight of citrate and 0.05 to 20% by weight of washing or cleaning-active polymers according to the claims. The amount of these builders can be limited in preferred process variants in favor of other washing and cleaning active substances.

In a first preferred embodiment, the phase or one of the phases of the washing or cleaning agent tablet according to the invention, 20 to 50 wt .-%, preferably 25 to 45 wt .-% and in particular 30 to 40 wt .-% sodium carbonate and / or sodium bicarbonate ,

In a second preferred embodiment, the phase or one of the phases of the washing or cleaning agent tablet according to the invention contains 15 to 55 wt .-%, preferably 20 to 50 wt .-% and in particular 25 to 40 wt .-% citrate.

In a third preferred embodiment, the phase or one of the phases of the detergent tablet according to the invention contains 0.5 to 15 wt.%, Preferably 1.0 to 10 wt.% And in particular 2 to 8 wt. or cleaning-active polymer from the group of amphoteric polymers.

Nonionic surfactants and enzymes are particularly suitable as further washing and cleaning-active ingredients of tablet phases according to the invention.

The addition of nonionic surfactant to the tablets (phases) of the invention improves their positive physical properties. This is especially true for amounts of surfactant to 5.0 wt .-%, preferably up to 4.0 wt .-%.

Preferred single-phase or multiphase washing or cleaning agent tablets according to the invention are therefore characterized in that the phase or one of the phases contains 0.5 to 10% by weight, preferably 1.0 to 8.0% by weight and in particular 2.0 to 6.0 wt .-% nonionic surfactant.

The compositions according to the invention may furthermore contain surfactants. The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is therefore given to ethoxylated nonionic surfactants consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow range ethoxylates" are particularly preferred.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred ,

The nonionic surfactants from the group of hydroxy mixed ethers have proved to be particularly advantageous with respect to the physical properties of the tablets (phases) according to the invention. These nonionic surfactants will be described below.

Surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _w - (A'O) _x - (A "O) _y - (A"'O) _z -R ² , in which R ¹ and R ² independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C _2-40 alkyl or alkenyl radical; A, A ', A "and A"' independently a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH ( CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² , in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.

Particularly preferred are surfactants of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.

By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another is a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y are independently from each other values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2 Butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand. When the value x ≥ 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,

Preferred single-phase or multiphase washing or cleaning agent tablets are furthermore characterized in that the phase or one of the phases contains less than 1.0% by weight and in particular no anionic surfactant, since the addition of anionic surfactants with respect to the tablets ( phase) properties, in particular their hardness, friability and post-curing has proved to be disadvantageous.

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

Washing or cleaning agent tablets (phases) which are preferred according to the invention are characterized in that they contain 1.0 to 22% by weight, preferably 2.0 to 20% by weight and in particular 5.0 to 18% by weight of enzyme preparation.

Some particularly preferred detergent tablets (phases) are listed in Tables A to E below. Table A Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] sodium 15 to 89.3 20 to 50 25 to 45 30 to 40 citrate 10 to 84.3 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 Misc 0 to 40 2 to 30 0 to 40 2 to 30 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] sodium 15 to 88.3 20 to 50 25 to 45 30 to 40 citrate 10 to 83.3 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 enzyme preparation 1.0 to 22 2.0 to 20 2.0 to 20 5, 0 to 18 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] sodium 15 to 89.2 20 to 50 25 to 45 30 to 40 citrate 10 to 84.2 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 Amylasezubereitung 0.1 to 10 0.2 to 8 0.2 to 8 0.5 to 6 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] sodium 15 to 88.3 20 to 50 25 to 45 30 to 40 citrate 10 to 83.3 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 protease preparation 1.0 to 20 2.0 to 18 2.0 to 18 5, 0 to 15 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] sodium 15 to 88.2 20 to 50 25 to 45 30 to 40 citrate 10 to 83.2 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 Amylasezubereitung 0.1 to 10 0.2 to 8 0.2 to 8 0.5 to 6 protease preparation 1.0 to 20 2.0 to 18 2.0 to 18 5, 0 to 15 * amphoteric copolymer

In a particularly preferred embodiment, the above-described tablet phase based on carbonate, citrate and polymer according to the invention is part of a two-phase or multi-phase detergent or cleaner tablet.

This two- or multi-phase detergent or cleaner tablet also contains washing and cleaning-active ingredients in its further phases, the composition of the further phases not being identical to the composition of the first tablet phase. In a preferred embodiment, the second tablet phase B further contains an oxygen bleach besides a carbonate based builder system.

1. i) eine erste Phase A, umfassend
   1. a) 15 bis 89,8 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
   2. b) 10 bis 84,8 Gew.-% Citrat
   3. c) 0,05 bis 20 Gew.-% wasch- oder reinigungsaktives Polymer aus der Gruppe der amphoteren Polymere
   4. d) kein Bleichmittel, weniger als 1 Gew.-%, vorzugsweise keine Citronensäure;
2. ii) eine zweite Phase B, umfassend
   • a) 15 bis 90 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
   • b) 10 bis 85 Gew.-% Sauerstoffbleichmittel
   • d) keine Enzyme

A particularly preferred two- or multi-phase detergent or cleaner tablet comprises

1. i) a first phase A comprising
   1. a) 15 to 89.8 wt .-% sodium carbonate and / or sodium bicarbonate
   2. b) 10 to 84.8 wt .-% citrate
   3. c) 0.05 to 20 wt .-% washing or cleaning-active polymer from the group of amphoteric polymers
   4. d) no bleach, less than 1% by weight, preferably no citric acid;
2. ii) a second phase B comprising
   • a) 15 to 90 wt .-% sodium carbonate and / or sodium bicarbonate
   • b) 10 to 85% by weight of oxygen bleach
   • d) no enzymes

As a preferred bleach machine dishwashing detergents according to the invention contain an oxygen bleaching agent from the group sodium percarbonate, Natriumperborattetrahydrat and Natriumperboratmonohydrat. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred.

A particularly preferred oxygen bleach is the sodium percarbonate.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) _2, [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Preferred washing or cleaning agent tablets according to the invention furthermore contain citric acid as further constituent of the second phase B described above. The content of citric acid in the second phase is preferably 1.0 to 15% by weight, preferably 2.0 to 12% by weight, and more preferably 4 to 8% by weight.

Detergent or detergent tablet, characterized in that the second phase B further contains c) 1.0 to 15 wt .-% citric acid, are preferred according to the invention.

Some particularly preferred detergent tablets (phases) are listed in Tables F to J below. Table F Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] Tablet phase 1 sodium 15 to 89.3 20 to 50 25 to 45 30 to 40 citrate 10 to 84.3 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 Misc 0 to 40 2 to 30 0 to 40 2 to 30 Tablet phase 2 sodium 15 to 90 20 to 50 25 to 45 30 to 40 sodium 10 to 85 10 to 70 10 to 55 10 to 40 Misc 0 to 40 2 to 30 0 to 40 2 to 30 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] Tablet phase 1 sodium 15 to 88.3 20 to 50 25 to 45 30 to 40 citrate 10 to 83.3 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 enzyme preparation 1.0 to 22 2.0 to 20 2.0 to 20 5, 0 to 18 Tablet phase 2 sodium 15 to 90 20 to 50 25 to 45 30 to 40 sodium 10 to 85 10 to 70 10 to 55 10 to 40 citric acid 0 to 30 1.0 to 15 1.0 to 15 1.0 to 15 Misc 0 to 40 2 to 30 0 to 40 2 to 30 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] Tablet phase 1 sodium 15 to 89.2 20 to 50 25 to 45 30 to 40 citrate 10 to 84.2 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 Amylasezubereitung 0.1 to 10 0.2 to 8 0.2 to 8 0.5 to 6 Tablet phase 2 sodium 15 to 90 20 to 50 25 to 45 30 to 40 sodium 10 to 85 10 to 70 10 to 55 10 to 40 citric acid 0 to 30 1.0 to 15 1.0 to 15 1.0 to 15 Misc 0 to 40 2 to 30 0 to 40 2 to 30 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] Tablet phase 1 sodium 15 to 88.3 20 to 50 25 to 45 30 to 40 citrate 10 to 83.3 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 protease preparation 1.0 to 20 2.0 to 18 2.0 to 18 5, 0 to 15 Tablet phase 2 Sodium (hydrogen) carbonate 15 to 90 20 to 50 25 to 45 30 to 40 sodium 10 to 85 10 to 70 10 to 55 10 to 40 citric acid 0 to 30 1.0 to 15 1.0 to 15 1.0 to 15 Misc 0 to 40 2 to 30 0 to 40 2 to 30 * amphoteric copolymer Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] Tablet phase 1 sodium 15 to 88.2 20 to 50 25 to 45 30 to 40 citrate 10 to 83.2 15 to 55 20 to 50 25 to 40 Polymer * 0.05 to 20 0.05 to 15 0.1 to 10 0.2 to 8.0 Nonionic surfactant 0.5 to 10 1.0 to 8.0 2.0 to 6.0 2.0 to 6.0 Amylasezubereitung 0.1 to 10 0.2 to 8 0.2 to 8 0.5 to 6 protease preparation 1.0 to 20 2.0 to 18 2.0 to 18 5, 0 to 15 Tablet phase 2 sodium 15 to 90 20 to 50 25 to 45 30 to 40 sodium 10 to 85 10 to 70 10 to 55 10 to 40 citric acid 0 to 30 1.0 to 15 1.0 to 15 1.0 to 15 Misc 0 to 40 2 to 30 0 to 40 2 to 30 * amphoteric copolymer

1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend, bezogen auf das Gesamtgewicht des teilchenförmigen Vorgemisches
   1. i) 15 bis 90 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
   2. ii) 10 bis 85 Gew.-% Citrat
   3. iii) kein Bleichmittel, weniger als 1 Gew.-%, vorzugsweise keine Citronensäure
   4. iv) optional weitere wasch- oder reinigungsaktive Bestandteile
2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend, bezogen auf das Gesamtgewicht der flüssigen Polymerzubereitung
   1. i) 40 bis 98 Gew.-% Wasser
   2. ii) 2 bis 60 Gew.-% wasch- oder reinigungsaktives Polymer
   3. iii) optional weitere wasch- oder reinigungsaktive Bestandteile auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs;
3. c) optional Zumischen weiterer wasch- oder reinigungsaktiver Substanzen;
4. d) Tablettierung des zweiten teilchenförmigen Vorgemischs, wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthalt.

A further subject of the present application is a process for the preparation of a phosphate-free washing or cleaning agent tablet, comprising the steps:

1. a) providing a first particulate premix containing, based on the total weight of the particulate premix
   1. i) 15 to 90 wt .-% sodium carbonate and / or sodium bicarbonate
   2. ii) 10 to 85% by weight citrate
   3. iii) no bleach, less than 1% by weight, preferably no citric acid
   4. iv) optional other washing or cleaning active ingredients
2. b) applying a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation
   1. i) 40 to 98 wt .-% water
   2. ii) 2 to 60 wt .-% washing or cleaning-active polymer
   3. iii) optionally further washing or cleaning active ingredients on the first particulate premix to obtain a second particulate premix;
3. c) optionally admixing further washing or cleaning-active substances;
4. d) tabletting of the second particulate premix, wherein the liquid polymer preparation comprises an amphoteric polymer.

The builder system used in step a) of the process according to the invention comprises 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 85% by weight of citrate.

1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend, bezogen auf das Gesamtgewicht des teilchenförmigen Vorgemisches
   1. i) 15 bis 90 Gew.-% Natriumcarbonat
   2. ii) 10 bis 85 Gew.-% Citrat
   3. iii) kein Bleichmittel, weniger als 1 Gew.-%, vorzugsweise keine Citronensäure
   4. iv) optional weitere wasch- oder reinigungsaktive Bestandteile
2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend, bezogen auf das Gesamtgewicht der flüssigen Polymerzubereitung
   1. i) 40 bis 98 Gew.-% Wasser
   2. ii) 2 bis 60 Gew.-% wasch- oder reinigungsaktives Polymer
   3. iii) optional weitere wasch- oder reinigungsaktive Bestandteile auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs;
3. c) optional Zumischen weiterer wasch- oder reinigungsaktiver Substanzen;
4. d) Tablettierung des zweiten teilchenförmigen Vorgemischs, wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthält,

ist damit ebenso Gegenstand der vorliegenden Anmeldung wie ein Verfahren zur Herstellung einer Phosphat-freien Wasch- oder Reinigungsmitteltablette, umfassend die Schritte:

1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend, bezogen auf das Gesamtgewicht des teilchenförmigen Vorgemisches
   1. i) 15 bis 90 Gew.-% Natriumhydrogencarbonat
   2. ii) 10 bis 85 Gew.-% Citrat
   3. iii) kein Bleichmittel, weniger als 1 Gew.-%, vorzugsweise keine Citronensäure
   4. iv) optional weitere wasch- oder reinigungsaktive Bestandteile
2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend, bezogen auf das Gesamtgewicht der flüssigen Polymerzubereitung
   1. i) 40 bis 98 Gew.-% Wasser
   2. ii) 2 bis 60 Gew.-% wasch- oder reinigungsaktives Polymer
   3. iii) optional weitere wasch- oder reinigungsaktive Bestandteile auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs;
3. c) optional Zumischen weiterer wasch- oder reinigungsaktiver Substanzen;
4. d) Tablettierung des zweiten teilchenförmigen Vorgemischs,

wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthält,
sofern in diesen Verfahren die Gesamtmenge des eingesetzten Natriumcarbonats und Natriumhydrogencarbonats bezogen auf das Gesamtgewicht des ersten teilchenförmigen Vorgemischs, 15 bis 90 Gew.-% beträgt.A process for making a phosphate-free detergent or detergent tablet, comprising the steps of:

1. a) providing a first particulate premix containing, based on the total weight of the particulate premix
   1. i) 15 to 90% by weight of sodium carbonate
   2. ii) 10 to 85% by weight citrate
   3. iii) no bleach, less than 1% by weight, preferably no citric acid
   4. iv) optional other washing or cleaning active ingredients
2. b) applying a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation
   1. i) 40 to 98 wt .-% water
   2. ii) 2 to 60 wt .-% washing or cleaning-active polymer
   3. iii) optionally further washing or cleaning active ingredients on the first particulate premix to obtain a second particulate premix;
3. c) optionally admixing further washing or cleaning-active substances;
4. d) tableting the second particulate premix, wherein the liquid polymer preparation comprises an amphoteric polymer,

is thus as subject of the present application as a A process for preparing a phosphate-free detergent or detergent tablet, comprising the steps of:

1. a) providing a first particulate premix containing, based on the total weight of the particulate premix
   1. i) 15 to 90 wt .-% sodium bicarbonate
   2. ii) 10 to 85% by weight citrate
   3. iii) no bleach, less than 1% by weight, preferably no citric acid
   4. iv) optional other washing or cleaning active ingredients
2. b) applying a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation
   1. i) 40 to 98 wt .-% water
   2. ii) 2 to 60 wt .-% washing or cleaning-active polymer
   3. iii) optionally further washing or cleaning active ingredients on the first particulate premix to obtain a second particulate premix;
3. c) optionally admixing further washing or cleaning-active substances;
4. d) tabletting of the second particulate premix,

wherein the liquid polymer preparation contains an amphoteric polymer,
inasmuch as in these processes the total amount of the sodium carbonate and sodium bicarbonate used, based on the total weight of the first particulate premix, is 15 to 90% by weight.

The first particulate premix provided in step a) contains the two constituents 15 to 90% by weight of sodium carbonate and / or sodium bicarbonate and 10 to 85% by weight of citrate. The amount of these builders can be limited in preferred process variants in favor of other washing and cleaning active substances.

In a first preferred variant of the process according to the invention, the first particulate premix, based in each case on its total weight, contains 20 to 50% by weight, preferably 25 to 45% by weight and in particular 30 to 40% by weight of sodium carbonate and / or sodium bicarbonate contains.

In a second preferred variant of the process according to the invention, the first particulate premix, based in each case on its total weight, contains 15 to 55% by weight, preferably 20 to 50% by weight and in particular 25 to 40% by weight of citrate.

As well as the amount of builders used in process step a), the amount of polymer and water used in process step b) can also be varied. As for the hardness, the decay and the abrasion properties of the tablets are advantageous in doing so inventive method in which the weight ratio of the first particulate premix to the liquid polymer preparation is between 150: 1 and 10: 1, preferably between 120: 1 and 14: 1 and in particular between 100: 1 and 17: 1.

With regard to the polymers used in the process of the invention, preference is given to those processes in which the polymer preparation applied in step b), based in each case on its total weight, contains from 5 to 50, preferably from 8 to 40 and in particular from 10 to 30,% by weight Contains polymer. It follows that the water content of the polymer preparation used in step b), in each case based on their total weight, preferably 50 to 95 wt .-%, preferably 60 to 92 wt .-% and in particular 70 to 90 wt .-% water.

The second particulate premix provided for tableting after step b) or after step c) of the process according to the invention preferably has a content of washing or cleaning-active polymer, preferably amphoteric polymer, of between 0.05 and 20% by weight. , preferably between 0.05 to 15 wt .-%, preferably between 0.1 to 10 wt .-% and in particular between 0.2 to 8 wt .-% to.

Of course, in addition to the builders and polymers described, other washing or cleaning-active substances can also be processed in the process according to the invention. These further washing- or cleaning-active substances may form part of the particulate premix provided in step a), but may alternatively or in addition also be part of the liquid polymer preparation applied in step b). According to the invention, it is furthermore preferred for further washing and cleaning-active substances to be added to the second particulate premix following step b) in a further process step c) before tableting.

• Verfahrensvariante A
  1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend, bezogen auf das Gesamtgewicht des teilchenförmigen Vorgemisches
     1. i) 15 bis 85 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
     2. ii) 10 bis 80 Gew.-% Citrat
     3. iii) kein Bleichmittel, weniger als 1 Gew.-%, vorzugsweise keine Citronensäure
     4. iv) 5 bis 75 Gew.-% weitere wasch- oder reinigungsaktive Bestandteile
  2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend, bezogen auf das Gesamtgewicht der flüssigen Polymerzubereitung
     1. i) 40 bis 96 Gew.-% Wasser
     2. ii) 2 bis 58 Gew.-% wasch- oder reinigungsaktives Polymer
     3. iii) optional 2 bis 58 Gew.-% weitere wasch- oder reinigungsaktive Bestandteile auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs;
  3. c) optional Zumischen weiterer wasch- oder reinigungsaktiver Substanzen;
  4. d) Tablettierung des zweiten teilchenförmigen Vorgemischs,
  wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthält.
• Verfahrensvariante B
  1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend, bezogen auf das Gesamtgewicht des teilchenförmigen Vorgemisches
     • i) 15 bis 85 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
     • ii) 10 bis 80 Gew.-% Citrat
     • iii) kein Bleichmittel, weniger als 1 Gew.-%, vorzugsweise keine Citronensäure
     • vi) optional 5 bis 75 Gew.-% weitere wasch- oder reinigungsaktive Bestandteile
  2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend, bezogen auf das Gesamtgewicht der flüssigen Polymerzubereitung
     1. i) 40 bis 96 Gew.-% Wasser
     2. ii) 2 bis 58 Gew.-% wasch- oder reinigungsaktives Polymer
     3. iii) 2 bis 58 Gew.-% weitere wasch- oder reinigungsaktive Bestandteile auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs;
  3. c) optional Zumischen weiterer wasch- oder reinigungsaktiver Substanzen;
  4. d) Tablettierung des zweiten teilchenförmigen Vorgemischs,
  wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthält.
• Verfahrensvariante C
  1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend, bezogen auf das Gesamtgewicht des teilchenförmigen Vorgemisches
     1. i) 15 bis 85 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
     2. ii) 10 bis 80 Gew.-% Citrat
     3. iii) kein Bleichmittel, weniger als 1 Gew.-%, vorzugsweise keine Citronensäure
     4. iv) optional 5 bis 75 Gew.-% weitere wasch- oder reinigungsaktive Bestandteile
  2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend, bezogen auf das Gesamtgewicht der flüssigen Polymerzubereitung
     1. i) 40 bis 96 Gew.-% Wasser
     2. ii) 2 bis 58 Gew.-% wasch- oder reinigungsaktives Polymer
     3. iii) optional 2 bis 58 Gew.-% weitere wasch- oder reinigungsaktive Bestandteile auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs;
  3. c) Zumischen weiterer wasch- oder reinigungsaktiver Substanzen;
  4. d) Tablettierung des zweiten teilchenförmigen Vorgemischs,
  wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthält.

Further preferred articles of the present application are therefore the following process variants for the preparation of a phosphate-free washing or cleaning agent tablet:

• Process variant A
  1. a) providing a first particulate premix containing, based on the total weight of the particulate premix
     1. i) 15 to 85 wt .-% sodium carbonate and / or sodium bicarbonate
     2. ii) 10 to 80 wt .-% citrate
     3. iii) no bleach, less than 1% by weight, preferably no citric acid
     4. iv) from 5 to 75% by weight of other washing or cleaning ingredients
  2. b) applying a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation
     1. i) 40 to 96 wt .-% water
     2. ii) 2 to 58% by weight of washing or cleaning-active polymer
     3. iii) optionally 2 to 58% by weight of further washing or cleaning active ingredients on the first particulate premix to obtain a second particulate premix;
  3. c) optionally admixing further washing or cleaning-active substances;
  4. d) tabletting of the second particulate premix,
  wherein the liquid polymer preparation contains an amphoteric polymer.
• Process variant B
  1. a) providing a first particulate premix containing, based on the total weight of the particulate premix
     • i) 15 to 85 wt .-% sodium carbonate and / or sodium bicarbonate
     • ii) 10 to 80 wt .-% citrate
     • iii) no bleach, less than 1% by weight, preferably no citric acid
     • vi) optionally 5 to 75 wt .-% of other washing or cleaning active ingredients
  2. b) applying a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation
     1. i) 40 to 96 wt .-% water
     2. ii) 2 to 58% by weight of washing or cleaning-active polymer
     3. iii) from 2 to 58% by weight of further detergent or cleaning ingredients on the first particulate premix to obtain a second particulate premix;
  3. c) optionally admixing further washing or cleaning-active substances;
  4. d) tabletting of the second particulate premix,
  wherein the liquid polymer preparation contains an amphoteric polymer.
• Process variant C
  1. a) providing a first particulate premix containing, based on the total weight of the particulate premix
     1. i) 15 to 85 wt .-% sodium carbonate and / or sodium bicarbonate
     2. ii) 10 to 80 wt .-% citrate
     3. iii) no bleach, less than 1% by weight, preferably no citric acid
     4. iv) optionally from 5 to 75% by weight of other washing or cleaning active ingredients
  2. b) applying a liquid polymer preparation containing, based on the total weight of the liquid polymer preparation
     1. i) 40 to 96 wt .-% water
     2. ii) 2 to 58% by weight of washing or cleaning-active polymer
     3. iii) optionally 2 to 58% by weight of further washing or cleaning active ingredients on the first particulate premix to obtain a second particulate premix;
  3. c) admixing further washing or cleaning-active substances;
  4. d) tabletting of the second particulate premix,
  wherein the liquid polymer preparation contains an amphoteric polymer.

The processes according to the invention are characterized in that the liquid polymer preparation b) contains an amphoteric polymer.

The group of amphoteric polymers and their inventively preferred representatives has already been described in detail above, which is why reference is made at this point to avoid repetition on the local statements.

Particularly preferred methods using amphoteric polymers are shown in Table 1 below.

Table 1

• Washing and cleaning-active polymer from step b)
• Copolymer of a diallyldimethylammonium salt
• Copolymer of a diallyldimethylammonium salt with acrylic acid
• Copolymer comprising
  1. i) 0.5 to 30 wt .-% diallyldimethylammonium salt
  2. ii) 70 to 99.5 wt .-% acrylic acid
• Copolymer of a Methyacrylamidopropyl-trimethylammonium salt
• Copolymer of a Methyacrylamidopropyl-trimethylammonium salt with acrylic acid
• Copolymer comprising
  1. i) 0.5 to 30 wt .-% Methyacrylamidopropyl trimethylammonium salt
  2. ii) 70 to 99.5 wt .-% acrylic acid

As previously stated, the first particulate premix, as well as the liquid polymer formulation applied in step b), may contain other detergent and cleaning active substances. At the same time or in addition thereto, these further washing and cleaning-active substances can also be added to the second particulate premix before tableting in the optional process step c).

The group of these other washing and cleaning-active substances include, for example, the surfactants, the enzymes and the fragrances or dyes.

Preferred processes according to the invention are characterized in that the particulate premix tableted in step d) contains 0.5 to 10% by weight, preferably 1.0 to 8.0% by weight and in particular 2.0 to 6.0% by weight. % nonionic surfactant (s) containing nonionic surfactants having a melting point above 30 ° C are particularly preferred.

Through the use of appropriate amounts of surfactant, the hardness and the decomposition and abrasion properties of the tablets produced according to the invention could be improved.

The group of surfactants and their inventively preferred representatives has already been described in detail above, which is why reference is made at this point to avoid repetition on the local statements.

The group of enzymes and their inventively preferred representatives has also already been described in detail above, which is why reference is again made to the statements there to avoid repetition at this point.

The enzymes are preferably incorporated into the premix before tableting in step c) of the process according to the invention.

The above-described methods and method variants according to the invention are preferably part of a multi-stage process for producing two-phase or multiphase washing or cleaning agent tablets.

In a first group of preferred methods according to the invention, the sodium carbonate, citrate and polymer according to the invention based on the claims tablet phases are pressed onto a prefabricated single- or multi-phase tablet.

• a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend
  1. i) 15 bis 90 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
  2. ii) 10 bis 85 Gew.-% Citrat
  3. iii) kein Bleichmittel und weniger als 1 Gew.-%, vorzugsweise keine Citronensäure;
• b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend
  1. i) 40 bis 98 Gew.-% Wasser
  2. ii) 2 bis 60 Gew.-% wasch- oder reinigungsaktives Polymer auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs und Aufbringen dieses zweiten teilchenförmigen Vorgemisches auf die Oberseite einer vorgefertigten ein- oder mehrphasigen Wasch- oder Reinigungsmitteltablette;
• d) Tablettierung des zweiten teilchenförmigen Vorgemischs auf die Oberseite der vorgefertigten ein- oder mehrphasigen Wasch- oder Reinigungsmitteltablette unter Ausbildung einer zwei- oder mehrphasigen Wasch- oder Reinigungsmitteltablette,

wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthält.A preferred process variant of this first group of processes for the preparation of a phosphate-free detergent or cleaner tablet comprises the steps:

• a) providing a first particulate premix containing
  1. i) 15 to 90 wt .-% sodium carbonate and / or sodium bicarbonate
  2. ii) 10 to 85% by weight citrate
  3. iii) no bleaching agent and less than 1% by weight, preferably no citric acid;
• b) applying a liquid polymer preparation containing
  1. i) 40 to 98 wt .-% water
  2. ii) from 2% to 60% by weight of detergent or cleaning active polymer on said first particulate premix to obtain a second particulate premix and applying said second particulate premix to the top of a preformed mono- or multi-phase detergent or detergent tablet;
• d) tableting the second particulate premix onto the top of the prefabricated single or multi-phase detergent or detergent tablet to form a two- or multi-phase detergent or detergent tablet;

wherein the liquid polymer preparation contains an amphoteric polymer.

1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend
   1. i) 15 bis 90 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
   2. ii) 10 bis 85 Gew.-% Citrat
   3. iii) kein Bleichmittel und weniger als 1 Gew.-%, vorzugsweise keine Citronensäure;
2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend
   1. i) 40 bis 98 Gew.-% Wasser
   2. ii) 2 bis 60 Gew.-% wasch- oder reinigungsaktives Polymer auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs
3. c) Zumischen weiterer wasch- oder reinigungsaktiver Substanzen und Aufbringen des resultierenden teilchenförmigen Vorgemisches auf die Oberseite einer vorgefertigten ein- oder mehrphasigen Wasch- oder Reinigungsmitteltablette;
4. d) Tablettierung des zweiten teilchenförmigen Vorgemischs auf die Oberseite der vorgefertigten ein- oder mehrphasigen Wasch- oder Reinigungsmitteltablette unter Ausbildung einer zwei- oder mehrphasigen Wasch- oder Reinigungsmitteltablette,

wobei die flüssige Polymer zubereitung ein amphoteres Polymer enthält.A second preferred process variant of this first group of processes for the preparation of a phosphate-free detergent or cleaner tablet comprises the steps:

1. a) providing a first particulate premix containing
   1. i) 15 to 90 wt .-% sodium carbonate and / or sodium bicarbonate
   2. ii) 10 to 85% by weight citrate
   3. iii) no bleaching agent and less than 1% by weight, preferably no citric acid;
2. b) applying a liquid polymer preparation containing
   1. i) 40 to 98 wt .-% water
   2. ii) 2 to 60% by weight of detergent or cleaning active polymer on the first particulate premix to give a second particulate premix
3. c) admixing further washing or cleaning-active substances and applying the resulting particulate premix to the top of a prefabricated mono- or multiphase washing or cleaning agent tablet;
4. d) tableting the second particulate premix onto the top of the prefabricated single or multi-phase detergent or detergent tablet to form a two- or multi-phase detergent or detergent tablet;

wherein the liquid polymer preparation contains an amphoteric polymer.

In a second group according to the invention more preferred. Processes are pressed onto the sodium carbonate, citrate and polymer according to the invention based on the claims tablet phases further single- or multi-phase tablet.

• a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend
  1. i) 15 bis 90 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
  2. ii) 10 bis 85 Gew.-% Citrat
  3. iii) kein Bleichmittel und weniger als 1 Gew.-%, vorzugsweise keine Citronensäure;
• b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend
  1. i) 40 bis 98 Gew.-% Wasser
  2. ii) 2 bis 60 Gew.-% wasch- oder reinigungsaktives Polymer auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs
• d) Tablettierung des zweiten teilchenförmigen Vorgemisches unter Ausbildung einer ersten Wasch- oder Reinigungsmitteltablette;
• e) Aufbringen eines weiteren, von den vorherigen teilchenförmigen Vorgemischen unterschiedlichen teilchenförmigen Vorgemisches auf die Oberseite der ersten Wasch- oder Reinigungsmitteltablette;
• f) Tablettierung des weiteren teilchenförmigen Vorgemisches unter Ausbildung einer zwei- oder mehrphasigen Wasch- oder Reinigungsmitteltablette;

A preferred process variant of this second group of processes for the preparation of a phosphate-free detergent or cleaner tablet comprises the steps:

• a) providing a first particulate premix containing
  1. i) 15 to 90 wt .-% sodium carbonate and / or sodium bicarbonate
  2. ii) 10 to 85% by weight citrate
  3. iii) no bleaching agent and less than 1% by weight, preferably no citric acid;
• b) applying a liquid polymer preparation containing
  1. i) 40 to 98 wt .-% water
  2. ii) 2 to 60% by weight of detergent or cleaning active polymer on the first particulate premix to give a second particulate premix
• d) tableting the second particulate premix to form a first detergent or cleaner tablet;
• e) applying a further, different from the previous particulate premix particulate premix on top of the first detergent or detergent tablet;
• f) tableting the further particulate premix to form a two- or multi-phase detergent or cleaner tablet;

1. a) Bereitstellen eines ersten teilchenförmigen Vorgemisches, enthaltend
   1. i) 15 bis 90 Gew.-% Natriumcarbonat und/oder Natriumhydrogencarbonat
   2. ii) 10 bis 85 Gew.-% Citrat
   3. iii) kein Bleichmittel und weniger als 1 Gew.-%, vorzugsweise keine Citronensäure;
2. b) Aufbringen einer flüssigen Polymerzubereitung, enthaltend
   1. i) 40 bis 98 Gew.-% Wasser
   2. ii) 2 bis 60 Gew.-% wasch- oder reinigungsaktives Polymer auf das erste teilchenförmige Vorgemisch unter Erhalt eines zweiten teilchenförmigen Vorgemischs
3. c) Zumischen weiterer wasch- oder reinigungsaktiver Substanzen
4. d) Tablettierung des zweiten teilchenförmigen Vorgemisches unter Ausbildung einer ersten Wasch- oder Reinigungsmitteltablette;
5. e) Aufbringen eines weiteren, von den vorherigen teilchenförmigen Vorgemischen unterschiedlichen teilchenförmigen Vorgemisches auf die Oberseite der ersten Wasch- oder Reinigungsmitteltablette;
6. f) Tablettierung des weiteren teilchenförmigen Vorgemisches unter Ausbildung einer zwei- oder mehrphasigen Wasch- oder Reinigungsmitteltablette;

A preferred process variant of this second group of processes for the preparation of a phosphate-free detergent or cleaner tablet comprises the steps:

1. a) providing a first particulate premix containing
   1. i) 15 to 90 wt .-% sodium carbonate and / or sodium bicarbonate
   2. ii) 10 to 85% by weight citrate
   3. iii) no bleaching agent and less than 1% by weight, preferably no citric acid;
2. b) applying a liquid polymer preparation containing
   1. i) 40 to 98 wt .-% water
   2. ii) 2 to 60% by weight of detergent or cleaning active polymer on the first particulate premix to give a second particulate premix
3. c) admixing further washing or cleaning active substances
4. d) tableting the second particulate premix to form a first detergent or cleaner tablet;
5. e) applying a further, different from the previous particulate premix particulate premix on top of the first detergent or detergent tablet;
6. f) tableting the further particulate premix to form a two- or multi-phase detergent or cleaner tablet;

A further subject of the present application is a washing or cleaning agent tablet produced by means of the method according to the invention.

Because of their good hardness, disintegration and abrasion properties, the detergent tablets according to the invention are particularly suitable for use in household dishwashers and textile washing machines.

A method for cleaning dishes in a dishwasher, using a detergent tablet according to the invention is a further subject of the present application.

Finally, a last subject of the present application is a process for textile cleaning in a textile washing machine using a detergent tablet according to the invention.

example

• V1: mit einer festen Polymerzubereitung
• V2: mit einer festen Polymerzubereitung und einer getrennt hiervon aufgebrachten Menge Wasser
• E1: mit einer Polymer-Wasser-Mischung beaufschlagt.

A. To prepare detergent tablets according to the invention, the following three premixes were prepared and pressed with a press force of 50 kN into single-phase tablets of 20 g total weight. V1 [% by weight] E1 [% by weight] E2 [% by weight] sodium 37.4 37.4 37.4 sodium citrate 30.3 33.3 33.3 citric acid 3.0 - - silicate 3.6 3.6 3.6 Amphoteric copolymer ^a) 2.2 2.2 2.2 Nonionic surfactant 3.2 3.2 4.1 Amylase preparation 2.7 2.7 2.7 Protease preparation 11.6 11.6 11.6 Misc, water ad 100 ad 100 ad 100 ^a) amphoteric copolymer of a Diallyldimethylammoniumsalzes with acrylic acid
^b) nonionic surfactant from the group of hydroxy mixed ethers
In the course of the preparation process, the caking tendency of the particulate premix, the tablet hardness and the friability of the tablets were determined. V1 E1 E2 Caking tendency * 4 1 2.5 Tablet hardness [N] <200 220 203 Tablet Friability [% by Weight] > 3 0.22 0.25 * Caking tendency: 1 (very low) to 4 (very high)
B. For carrying out the process according to the invention, a first particulate premix was used

• V1: with a solid polymer preparation
• V2: with a solid polymer preparation and a separately applied amount of water
• E1: applied with a polymer-water mixture.

The second particulate preparation thus obtained was then blended with nonionic surfactant, silicate, enzymes and ingredients. The exact composition of the tablet premix resulting therefrom can be found in the following table: V1 [% by weight] V2 [% by weight] E1 [% by weight] premix sodium 39.4 37.6 37.6 citrate 27.3 27.3 27.3 polymer solution amphoteric polymer ^a) 0.4 0.4 * 0.4 ** water - 1.8 * 1.8 ** admixture Nonionic surfactant ^b) 3.8 3.8 3.8 silicate 3.6 3.6 3.6 enzymes 14.0 14.0 14.0 Misc ad 100 ad 100 ad 100 ^a) amphoteric copolymer of a Diallyldimethylammoniumsalzes with acrylic acid
^b) nonionic surfactant from the group of hydroxy mixed ethers
* Polymer and water are applied separately
** Polymer and water are applied in the form of a polymer-water mixture.

The resulting tablet premixes were pressed at a pressing force of 55 N into tablets weighing 21 g. V1 V2 E1 Tablet hardness [N] ¹⁾ 196 201 195 Tablet hardness [N] ²⁾ 287 342 375 Friability [% by weight] 0.48 0.15 0.12 ¹⁾ Tablet hardness immediately after tableting
²⁾ Tablet hardness after 3 days storage

As can be seen from the data obtained, the tablets produced by the process according to the invention by addition of a polymer-water mixture harden significantly more vigorously than the tablets prepared in the comparative experiments with the addition of solid polymer preparations at the same pressure and achieve an overall higher overall hardness.

Claims (13)

1. Single- or multi-phase phosphate-free detergent or cleaning agent tablet, characterized in that the phase or one of the phases, based on its total weight, contains

   a) 15 to 89.8% by weight of sodium carbonate and/or sodium hydrogen carbonate

   b) 10 to 84.8% by weight of citrate

   c) 0.05 to 20% by weight of polymer having washing or cleaning activity,

   is free of bleaching agent, and contains less than 1% by weight of citric acid, based on the total weight of the phase, wherein the polymer c) having washing or cleaning activity encompasses a polymer from the group of amphoteric polymers.
2. Detergent or cleaning agent tablet according to Claim 1, characterized in that the phase or one of the phases contains 20 to 50% by weight, preferably 25 to 45% by weight, and in particular 30 to 40% by weight of sodium carbonate and/or sodium hydrogen carbonate.
3. Detergent or cleaning agent tablet according to one of the preceding claims, characterized in that the phase or one of the phases contains 15 to 55% by weight, preferably 20 to 50% by weight, and in particular 25 to 40% by weight of citrate.
4. Detergent or cleaning agent tablet according to one of the preceding claims, characterized in that the phase or one of the phases contains 0.05 to 15% by weight, preferably 0.1 to 10% by weight, and in particular 0.2 to 8% by weight of polymer having washing or cleaning activity from the group of amphoteric polymers, wherein the total quantity of polymer having washing or cleaning activity is in each case likewise within the stated range.
5. Detergent or cleaning agent tablet according to one of the preceding claims, characterized in that the phase or one of the phases contains 0.5 to 10% by weight, preferably 1.0 to 8.0% by weight, and in particular 2.0 to 6.0% by weight of nonionic surfactant.
6. Detergent or cleaning agent tablet according to one of the preceding claims, characterized in that the phase or one of the phases contains 1.0 to 22% by weight, preferably 2.0 to 20% by weight, and in particular 5.0 to 18% by weight of enzyme preparation.
7. Detergent or cleaning agent tablet, comprising

   i) a first phase A, comprising

   a) 15 to 89.8% by weight of sodium carbonate and/or sodium hydrogen carbonate

   b) 10 to 84.8% by weight of citrate

   c) 0.05 to 20% by weight of polymer having washing or cleaning activity from the group of amphoteric polymers

   d) no bleaching agent and less than 1% by weight of citric acid;

   ii) a second phase B, comprising

   a) 15 to 90% by weight of sodium carbonate and/or sodium hydrogen carbonate

   b) 10 to 85% by weight of oxygen bleaching agent

   d) no enzymes.
8. Detergent or cleaning agent tablet according to Claim 7, characterized in that the second phase B further contains

   c) 1.0 to 30% by weight of citric acid.
9. Method for manufacturing a phosphate-free detergent or cleaning agent tablet, comprising the following steps:

   a) providing a first particulate premixture containing

   i) 15 to 90% by weight of sodium carbonate and/or sodium hydrogen carbonate

   ii) 10 to 85% by weight of citrate

   iii) no bleaching agent and less than 1% by weight of citric acid;

   b) applying a liquid polymer preparation containing

   i) 40 to 98% by weight of water

   ii) 2 to 60% by weight of polymer having washing or cleaning activity to the first particulate premixture to obtain a second particulate premixture;

   d) tableting of the second particulate premixture to form a detergent or cleaning agent tablet,

   characterized in that the liquid polymer preparation b) contains an amphoteric polymer.
10. Method according to Claim 9, characterized in that the weight ratio of the first particulate premixture to the liquid polymer preparation is between 150:1 and 10:1, preferably between 120:1 and 14:1, and in particular between 100:1 and 17:1.
11. Method according to one of the preceding claims, characterized in that the particulate premixture tableted in step d) contains 0.5 to 10% by weight, preferably 1.0 to 8.0% by weight, and in particular 2.0 to 6.0% by weight of nonionic surfactant(s).
12. Method according to one of the preceding claims, characterized in that following step b), further substances having washing or cleaning activity are mixed into the second particulate premixture in a further method step c) prior to the tableting.
13. Method for cleaning dishware in a dishwasher, using a machine dishwasher detergent according to one of Claims 1 to 8.